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Publication numberUS2363464 A
Publication typeGrant
Publication dateNov 21, 1944
Filing dateApr 29, 1942
Priority dateApr 29, 1942
Publication numberUS 2363464 A, US 2363464A, US-A-2363464, US2363464 A, US2363464A
InventorsSenkus Murray
Original AssigneeCommercial Solvents Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Beta-aminoalkyl acetals
US 2363464 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented Nov. 21, 1944 UNITED STATES PATENT OFFICE v v 2,363,464 I BETA-AMINOALKYL ACETALS Murray Senku's, Terre Haute, Ind., assignor to Commercial Solvents Corporation, Terre Haute,

Ind., a corporation of Maryland I No Drawing. Application April 29, 1942,

Serial N0. 441,022

7Ulain1s. (or. 260-584) My invention relates to new and useful amino acetals. MOI'e particularly, it is concerned with symmetrical beta-aminoalkyl acetals having th following general structural formula: j

wherein R may represent hydrogen or alkyl, and R may represent a member selected from the group consisting of hydrogen, alkyl, and aryl., Examples of the beta-aminoal kyl acetals included within the scope of my invention, are the bis(2- amino=2-methylpropoxy)methanes, and the bis- (2-aminobutoxy) methanes which have the following structural formulas:

wherein R may represent hydrogen or alkyl, and R may be either hydrogen, alkyl, or aryl.

The beta-aminoalkyl acetals of my invention are preferably prepared by the catalytic hydrogenation of the corresponding nitro compounds. According to this process, the desired nitro compound is subjected to hydrogenation at normal or elevated pressures in the presence of a hydrogenationcatalyst, with or without an auxiliary solvent, such as methanol or an aqueous solution of carbon dioxide, at a temperature below 125 C. In general, any hydrogenationcatalyst which possesses catalytic activity under the conditions employed, will be satisfactory. I prefer, however, to use a finely-divided Raney nickel catalyst. This catalyst, is very active in hydrogenation processes of this type, and has an exceptionally long life, I

The hydrogenation reaction in general may be effected at hydrogen pressures ranging from atmospheric pressure to pressures slightly below, those which tend to cleave the acetal linkage. I 'havefound it preferable, however, to carry out such reactions at pressures ranging from approximately 1000 to 1500 pounds per square inch, and at a temperature of from about 50 to '70 C., in the presence of thorough agitation. The rate of reaction is directly proportional 'to the temperatures and pressures utilized and, therefore,for a decrease in one of them, there should be a corresponding increase in the other. Lower term from two to four hours.

peratures and pressures will ordinarily require a longer reaction time and, conversely, higher pressures and temperatures will in general shorten the time for completion of the reaction. However, under the latter conditions excessive pres-. sures and/or temperatures, even with a shortreaction period, tend to result in lower yields of the desired amino compound. When carrying out thereaction in accordance with the preferred conditions described above, hydrogenation is in general found to be complete after a period of Optimum conditions in regard to the temperature, pressure, and catalyst in any given instance, however, may be readily determined by simple experiment. Also, it is generally desirable to employ a suitable solvent such as methyl or ethyl alcohol.

When hydrogen is no longer absorbedand the reaction is complete, the catalyst isseparated from the reaction mixture and the solventsolution fractionated, to yield the beta-aminoalkyl acetals. 'The products obtained in this manner are, in general, relatively pure. if it is desired to purify these materials further, however, they may be distilled under reduced pressure. In order to facilitate their separation from the reaction mixture, it is sometimes desirable to agitate the reaction mixture with a caustic solution, and extract the beta-aminoalkyl acetals with ether. Fractionation of the ether extract yields the betaaminoalkyl acetals.

The dinitro acetals employed in the prepara-,

which is capable of removing the water produced during the reaction, in the form of a. constant boiling mixture. I have found this reactionto be very general in character and may be effected between any aldehyde and 'nitro alcohol of the type herein disclosed. Suitable aldehydes, which may be employed in this reaction, are formalde-, hyde, isobutyraldehyde, benzaldehyde, heptaldehyde, acrylic aldehyde, and the like. As examples of nitro alcohols which may be utilized, there ay be mentioned 2-nitro-2-methyl-1-propanol,

2-nitrovl-butanol, 3-nitro-3-methyl-2-butanol,

Z-nitro-l-pentanol, 3-nitro-2-pentanol, and the Example I One hundred and twenty parts of bis(2-nitro- 2-methylpropoxy)methane, 80 parts of methyl alcohol, and 2 parts of Raney nickel catalyst were placed in a suitable hydrogenation apparatus and sealed. This solution was hydrogenated at a pressure of 1400 pounds per square inch at 60 C. for a period of two hours with constant agitation. After absorptionof the hydrogen had ceased, the reaction mixture was withdrawn from the hydrogenation apparatus, the catalyst removed by filtration, and the filtrate fractionated. The bis(2-amin0 2 methylpropoxy) methane, thus obtained, amountedto 88 parts, corresponding to a 96 per cent yield and was substantially free from impurities. The relatively colorless, odorless liquid obtained in this manner distilled at 72-74 C. at 2 mm. pressure.

Analysis: Calculated for C9H22N2O2: N, 14.74;

neutral equivalent, 95. Found: N, 14.73; neutral equivalent, 96.

Example II 2-methyl-1,1-bis(2-amino 2 methylpropoxy) propane was prepared by dissolving 14 parts of 2 methyl-1,1-bis(2-nitro-2-methylpropoxy) pro pane in 80 parts of methyl alcohol and hydrogenating the mixture in the presence of 2 parts of Raney nickel catalyst for two hours at 60 C. under a pressure of 1500 pounds per square inch. The corresponding amino compound was obtained in 91 per cent yield and distilled at 92 C. at 2 mm. pressure. I

Analysis: Calculated for C12H2BN202I N, 12.07;

neutral equivalent, 116. Found: N, 12.17; neu-f tral equivalent, 116.

Example III Eighteen parts of bis(2-nitro-2-methylpropoxy)phenylmethane, 120 parts of methyl a1- cohol and parts of Raney nickel catalyst were placed in a hydrogenation apparatus and sub jected to hydrogenation for four hours at a temperature of 70 C., according to the procedure of Example I. The resulting product, bis(2-amino- 2 methylpropoxy) phenylmethane distilled at 121-122 C., at 2 mm. pressure, and was obtained in a yield of 90 per cent.

Analysis: Calculated for CH26N2O2Z N, 10.53; neutral equivalent, 133. tral equivalent, 134.

Example IV Found: N, 10.74; neu-- neutral equivalent, 109. Found: N, 13.07; neutral equivalent, 109.

Example V A mixture consisting of parts of bis(2-nitrobutoxy) methane, 150 parts of water, parts of solid carbon dioxide and 10 parts of Raney nickel catalyst was hydrogenated for two hours at 70 C, and 1900 pounds per square inch, according to the process of Example I. The reaction solution was filtered and the filtrate agitated with 100 parts of a 44 per cent caustic solution. This alkaline mixture was then extracted with three 90-part portions of ether. Fractionation of the ether extract yielded 36 parts of bis(2-aminobul. Symmetrical beta-ami-noalkyl acetals having the structural formula:

wherein R represents a member selected from the group consisting of hydrogen and alkyl, and R represents a member selected from the group consisting of hydrogen, alkyl, and aryl.

2. Bis(2-amino-2-methylpropoxy) methane.

3. Bis(2-aminobutoxy)methane.

4. Z-methyl- 1,1 bis(2 amino 2 methylpropoxy) propane.

5. In a process for the direct catalytic hydro genation of a beta-nitroalkyl acetal to the corresponding beta-aminoalkyl acetal, the step which comprises subjecting a, beta-nitroalkyl acetal to hydrogenation in the liquid phase in the presence of a hydrogenation catalyst at a temperature below 125 C. and under pressure of from about 1000 to 2000 pounds.

6. In a process for the direct catalytic hydrogenation of a beta-nitroalkyl acetal to the correspondin beta-aminoalkyl acetal, the step which comprises subjecting a beta-nitroalkyl acetal to hydrogenation in the liquid phase in the presence of a hydrogenation catalyst at elevated temperatures and pressures.

7. In a process for the direct catalytic hydrogenation of a beta-nitro-alkyl acetal having nitrogen and hydrogen attached to the same carbon atom to the corresponding beta-aminoalkyl acetal, the step which comprises subjecting a beta-nitro-alkyl acetal to hydrogenation in the presence of a hydrogenation catalyst and an aqueous solution of carbon dioxide at elevated temperatures and pressures.

MURRAY SENKUS.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2673880 *Aug 7, 1951Mar 30, 1954Commercial Solvents CorpProduction of amino hydroxy compounds
US3862227 *Jun 15, 1972Jan 21, 1975Ciba Geigy CorpNew diamines
US7183874 *Feb 1, 2005Feb 27, 2007Ntt Docomo. Inc.Casing contained filter
US7569719Oct 24, 2007Aug 4, 2009Loctite (R&D) LimitedMethod of preparing electron deficient olefins
US7659423Apr 18, 2006Feb 9, 2010Loctite (R&D) LimitedMethod of preparing electron deficient olefins in polar solvents
US7718821Dec 19, 2006May 18, 2010Loctite (R&D) LimitedMethod of preparing electron deficient olefins
US7973119Jul 5, 2011Loctite (R&D) LimitedAdhesive systems using imines and salts thereof and precursurs to electron deficient olefins
US8053589Nov 8, 2011Henkel Ireland LimitedImines and methods of preparing electron deficient olefins using such novel imines
US8399698Oct 22, 2009Mar 19, 2013Henkel Ireland LimitedSubstituted activated methylene reagents and methods of using such reagents to form electron deficient olefins
US8481755Apr 23, 2010Jul 9, 2013Henkel Ireland Ltd.Activated methylene reagents and curable compositions prepared therefrom
US8697915 *Dec 15, 2010Apr 15, 2014Angus Chemical CompanyDiamino-alcohol compounds and processes for their manufacture
US20050184826 *Feb 1, 2005Aug 25, 2005Ntt Docomo, Inc.Filter
US20100199888 *Apr 23, 2010Aug 12, 2010Loctite (R&D) LimitedActivated methylene reagents and curable compositions prepared therefrom
US20100210788 *Apr 23, 2010Aug 19, 2010Loctite (R&D) LimitedElectron deficient olefins
US20110152574 *Dec 15, 2010Jun 23, 2011Peera Asghar ANovel diamino-alcohol compounds and processes for their manufacture
EP1546227A2 *Aug 29, 2003Jun 29, 2005Huntsman Petrochemical CorporationPolyether polyamine agents and mixtures therefor
Classifications
U.S. Classification564/495, 564/497, 564/346, 564/504, 564/358
Cooperative ClassificationC07C205/15